EP1735416A1

EP1735416A1 - Detergent and cleaning agents containing dye fixatives and soil-release polymers

Info

Publication number: EP1735416A1
Application number: EP05733430A
Authority: EP
Inventors: Michael Wessling; Frank-Peter Lang
Original assignee: Clariant Produkte Deutschland GmbH
Current assignee: Clariant Produkte Deutschland GmbH
Priority date: 2004-04-08
Filing date: 2005-04-06
Publication date: 2006-12-27
Also published as: WO2005097959A1; JP2007532706A; US20070277327A1; DE102004018051A1

Abstract

The invention relates to detergents and cleaning agents that contain both a dye fixative and a soil-release polymer. According to the invention, the dye fixatives used are (a) reaction products of polyamines and cyanamides and organic and/or inorganic acids, or cyanamides and aldehydes and ammonium salts, or cyanamides and aldehydes and amines, or amines and epichlorohydrin, (b) the group containing polyamines and polyamine derivatives, (c) the group containing polyimines and polyimine derivatives, (d) the group of cationic polyelectrolytes, (e) the group containing polymers that comprise imidazoline units or (f) the group containing bis(chloromethyl)biphenyl polyquat.

Description

description

Detergents and cleaning agents containing color fixatives and soil release polymers

The invention relates to detergents and cleaning agents which contain a combination of one or more color fixing agent (s) and one or more soil release polymer (s).

A known problem with washing colored textiles is that they fade over several washing cycles. This problem occurs particularly with dark-colored textiles made of cotton and cotton blended fabrics. In the case of well-fixed textile dyes, this process takes place over a longer period of use. If, on the other hand, the dyes of a dyed textile are poorly fixed, that is to say the textile "bleeds", not only does the colored textile fade quickly, but it can also, due to the relatively high dyestuff concentrations in the wash liquor, also stain other colors or those washed with it white textiles come in. In any case, colored textiles lose their new appearance relatively quickly, which limits the useful life of the textile.

In order to solve the problem of bleeding out or fading of colored textiles, the use of so-called color fixing agents is proposed in the literature. WO 98/29529 claims detergents which contain at least one anionic surfactant, an organic or inorganic builder and a color fixing agent. The color fixatives used must not react with the anionic surfactant. WO 96/27649 claims detergent formulations which contain a combination of a cationic color fixing agent and a cellulase. WO 01/44423 describes the claim to laundry care formulations which contain a color fixing agent, an N-heterocyclic polymer and a nonionic surfactant. Compounds known as color transfer inhibitors, such as polyvinylpyrrolidone, are listed as N-heterocyclic polymers. EP 1 239 025 and EP 1 236 793 describe detergents and laundry treatment compositions which contain color transfer-inhibiting color fixing agents.

However, one problem with all color fixatives is that they increase the redeposition of detached, particulate dirt from the wash liquor on the textile and thus promote the graying of the laundry. This problem is particularly pronounced in the case of the cationic color fixing agents. But it can occur with all color fixatives.

It is also known to use so-called soil release polymers in laundry detergents and cleaning agents for textiles to improve the detachment of dirt from synthetic fibers, in particular polyester and polyester blended fabrics. These soil release polymers are water-soluble or water-dispersible polycondensates based on dicarboxylic acids and diols or cellulose ethers.

The purpose of the present invention is to provide washing and cleaning agent formulations which contain one or more color fixing agents and which, compared to the corresponding reference formulations without color fixing agents, do not result in an increased dirt reduction position.

It has now surprisingly been found that this goal can be achieved by combining the color fixer (s) with one or more soil release polymers.

The subject of the invention are

Washing and cleaning agents containing one or more color fixatives from the group

a) reaction products of Polyamines with cyanamides and organic and / or inorganic acids or cyanamides with aldehydes and ammonium salts or cyanamides with aldehydes and amines ¹ or amines with epichlorohydrin

b) the group of polyamines and polyamine derivatives,

c) the group of polyimines and polyimine derivatives,

d) the group of cationic polyelectrolytes,

e) the group of polymers containing imidazoline units or f) the group of bischlormethylbiphenyl polyquats

and a soil release polymer.

The color fixatives that can be used in the combinations described with soil release polymers are anionic, nonionic or cationic and are described below:

Polycondensates that can be used as color fixatives are obtained by reacting polyamines with cyanamides and organic or inorganic acids, by reacting cyanamides with aldehydes and ammonium salts and / or amines, or by reacting amines with epichlorohydrin.

Polyamines or their derivatives can also be used as color fixatives. Such polyamines can have the general structure

H ₂ N - R ¹ - (NH - R ² ) _n - NH ₂

have, where R1 and R2 are linear or branched C 1 -C ₄ alkylene, such as ethylene, propylene, butylene and n is an integer from 0 to 1000. Examples of polyamines are diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA), dipropylenetriamine. The polyamines can also be branched via tertiary nitrogen atoms. Polyamine derivatives are in particular amine alkoxylates, such as amine ethoxylates,

Amine oxides, betaines and quaternary ammonium salts. The polyamine derivatives are obtained by completely or partially reacting the polyamines with alkylene oxides, in particular ethylene oxide, with hydrogen peroxide, with halocarboxylic acids, such as, for example, Chloroacetic acid or chloropropionic acid and / or with alkylating agents such as e.g. Methyl chloride, dimethyl sulfate or benzyl chloride. Polymers that can also be used as color fixatives are polyethyleneimines. These are e.g. available from BASF under the trade name Lupasol.

Cationic polyelectrolytes can also be used as color fixatives.

This is e.g. to homopolymers and copolymers based on diallyl dimethyl ammonium chloride (DADMAC).

Copolymers based on DADMAC contain other vinyl monomers such as e.g. Vinylimidazole, vinylpyrrolidone, vinyl alcohol,

Vinyl acetate, (meth -) - acrylic acid (ester) and acrylamide. Such polymers are available, for example, under the trade names Agefloc, Agequat and Tinofix, such as e.g. Agefloc WT 40, Agefloc WT 40 SV, Agefloc WT 40 SVL and Tinofix FRD

(from Ciba SC).

Homopolymers based on DADMAC are available under the trade names Dodigen 3954, Dodigen 4033 and Genamin PDAC (from Clariant). Further Polymers based on vinyl monomers may contain acrylamidomethyl propanesulfonic acid (AMPS).

Basic polycondensates with imidazoline units as described in WO 01/74982 can also be used as color fixing agents.

Bischlormethylbiphenylpolyquats can also be used, as described in DE 2 657 582 and EP 225 281.

Other color fixatives include: Levogen and Lavafix brands (Bayer), Gafquat brands (ISP), Neofix brands (Nicca), the Sevofix brands (Textile Color) and the Tinofix brands, e.g. Tinofix CL, Tinofix ULC, Tinofix ECO, Cibafix ECO and Solfix E (Ciba SC). TexCare DFC brands (Clariant) are particularly preferred as color fixatives.

Soil release polymers which can be used together with color fixatives are, for example, cellulose ethers or polycondensates based on dibasic carboxylic acids and starting materials which have two or more hydroxyl groups. Terephthalic acid is usually used as the dibasic carboxylic acid.

These soil release polymers can be nonionic or anionic.

Nonionic soil release polymers and their use in detergents and cleaning agents are e.g. described in US 4,116,885, EP 185427, EP 442 101, DE 4403 866, DE 19522431 and EP 964 015.

The following structural formulas give an example of the chemical structure of nonionic soil release polymers:

Figure 1: Soil Release Polymer

Soil Release Polymer I:

R ¹ and R ⁷ linear or branched -CC ₈ alkyl R ² , R ⁴ , R ⁶ alkylene, for example ethylene, propylene, butylene R ³ and R ⁵ 1, 4-phenylene, 1, 3-phenylene A, B and D a number between 1 and 200 C a number between 1 and 20

o 0 Q

R ¹ - (θ-R ² ) _x - O- CR ³ -CO- (R ⁴ -0) ₂ C-R3-COR ⁵ -O- CR ³ -C-0- (R ⁶ -O) _y R

Figure 2: Soil Release Polymer II Soil Release Polymer II:

R ¹ and R ^{7 are} linear or branched d-cis-alkyl,

R ² and R ⁶ ethylene,

R ³ 1, 4-phenylene,

R ⁴ ethylene,

R ⁵ ethylene, 1, 2-propylene or statistical mixtures of any composition of both, x and y independently of one another a number between 1 and 500, z a number between 10 and 140, a a number between 1 and 12, b a number between 7 and 40, where a + b is at least 11.

Preferably, independently of one another, R ¹ and R ^{7 are} linear or branched CrC alkyl, x and y are a number between 3 and 45, z a number between 18 and 70, a a number between 2 and 5, b a number between 8 and 12, a + b a number between 12 and 18 or between 25 and 35.

Anionic soil release polymers are e.g. described in US 4,721,580, WO 95/02028, WO 95/02029, EP 707 627, US 5,691, 298, US 5,700,386, US 5,843,878 and WO 96/18715.

As anionic monomers for the preparation of the oligomers or polyesters, in addition to the aforementioned monomers, e.g. Hydroxyethanesulfonic acid (isethionic acid), hydroxypropanesulfonic acid, their reaction products with ethylene oxide, glycerol sulfoethyl ether and sulfoisophthalic acid.

In these esters, preference is given to those which have the following features: polyester with a molecular weight of less than 20,000, preferably less than 10,000 and very particularly preferably less than 5,000; Polyesters which are end-capped using alkyl polyalkylene glycols; Polyesters which are end-capped by means of methyl polyethylene glycols, the number of ethylene glycol units being </ = 90, preferably </ = 50 and particularly preferably </ = 20; Polyesters which preferably have </ = 60% by mass and particularly preferably </ = 50% by mass of esterified terephthalic acid units; Polyesters containing ethylene glycol or polyethylene glycol units; Polyesters containing propylene glycol or polypropylene glycol units; Polyester, which is both ethylene glycol or polyethylene glycol, as well as propylene glycol or

Contain polypropylene glycol units; Polyesters that are anionically modified using condensed sulfoisophthalic acid units.

Cellulose ethers are also suitable as soil release polymers, preferably those with a molecular weight of less than 150,000. Examples of these are methyl cellulose, methyl hydroxycellulose and methyl hydroxypropyl cellulose. Commercial soil release polymers are marketed under the trade names Repel-O-Tex, such as Repel-O-Tex SRP 4, Repel-O-Tex SRP 6, Repel-O-Tex PF, Repel-O-Tex PF 594 (Rhodia ), Sokalan, such as Sokalan SR 100 (from BASF), Marloquest, such as Marloquest SL (Sasol) and TexCare, such as TexCare SRN-170, TexCare SRN-240 and TexCare SRN-325 (from Clariant) offered.

The active compound combination according to the invention is preferably used in an application concentration of 0.1 to 20% by weight, preferably 0.1 to 10% by weight and particularly preferably 0.1 to 5% by weight, very particularly preferably 0.3 up to 3% by weight, based on the washing and cleaning agents.

The preferred weight ratio of color fixing agent to soil release polymer is 1:10 to 10: 1, preferably 1: 5 to 5: 1.

The detergent formulations in which the combinations of color fixative (s) and soil release polymer (s) according to the invention can be used are in the form of powders, granules, pellets, tablets, laundry items (“bars”, “blocks”), pastes, gels or liquids in front. These forms can be packed in foils that either have a protective function during storage or also serve as a metering aid. The films can be water-soluble.

The color fixative (s) and soil release polymer (s) can also be applied in a procedure in which one of the two components is separate from the detergent formulation and the wash cycle is metered in separately.

However, the combination of a color fixative and a soil release polymer can also be provided separately from the actual detergent formulation and added to the wash if necessary.

The combination of a color fixing agent and a soil release polymer according to the invention can also be used in laundry pretreatment and aftertreatment agents or in washing boosters. Laundry after-treatment agents are laundry conditioners, such as fabric softener. Detergents and cleaning agents which contain the active ingredient combination according to the invention can also contain further constituents. These are described below.

Anionic surfactants

Suitable anionic surfactants are sulfates, sulfonates, carboxylates, phosphates and mixtures thereof. Suitable cations are alkali metals, e.g. Sodium or potassium or alkaline earth metals, such as e.g. As calcium or magnesium and ammonium, substituted ammonium compounds, including mono-, di- or triethanolammonium cations, and mixtures thereof.

The following types of anionic surfactants are particularly preferred:

Alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, alkane sulfonates and soaps as described below.

Alkyl ester sulfonates include linear esters of Cs-C ₂ o-carboxylic acids (ie fatty acids) which are sulfonated using gaseous SO, as described in "The Journal of the American Oil Chemists Society" 52 (1975), pp. 323-329.

Suitable starting materials are natural fats such as e.g. Tallow, coconut oil and palm oil can also be synthetic.

Preferred alkyl ester sulfonates, especially for detergent applications, are compounds of the formula

R ¹ CH COOR

S0 _{3 s}

wherein R ^{1 is} a C ₈ -C ₂ o-hydrocarbon radical, preferably alkyl, and R is a C ₁ -C ₆ hydrocarbon radical, preferably alkyl. M stands for a cation that forms a water-soluble salt with the alkyl ester sulfonate. Suitable cations are Sodium, potassium, lithium or ammonium cations such as monoethanolamine, diethanolamine and triethanolamine. R ^{1 is} preferably C ¹ -C 6 -alkyl and R is methyl, ethyl or isopropyl. Methyl ester sulfonates in which R ^{1 is} C ¹ -C ₆ -alkyl are particularly preferred.

Alkyl sulfates here are water-soluble salts or acids of the formula ROS0 ₃ M, in which R is a Cιo-C ₂₄ hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with a Cιo-C _2u alkyl component, particularly preferably a C ₁ 2-C ₁ 8 alkyl or Hydroxyaikylrest is. M is hydrogen or a cation, for example an alkali metal cation (for example sodium, potassium, lithium) or ammonium or substituted ammonium, for example methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof.

Alkyl chains of C ₁₂ -C ₁₆ are preferred for lower wash temperatures (eg below about 50 ° C) and alkyl chains of C ₁₆ -C ₁ 8 for higher wash temperatures (eg above about 50 ° C).

Alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) _m SO3M, in which R is an unsubstituted C 1 -C ₄ -alkyl or hydroxyalkyl radical, preferably a C ₁₂ -C ₂₀ alkyl or hydroxyalkyl radical, particularly preferably Ci ₂ -Cιβ- Represents alkyl or hydroxyalkyl radical. A is an ethoxy or propoxy unit, m is a number greater than 0, preferably between approximately 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3, and M is a hydrogen atom or a cation such as, for example Sodium, potassium, lithium, calcium, magnesium, ammonium or a substituted ammonium cation. Specific examples of substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof. Examples include C ₁₂ to cis fatty alcohol ether sulfates wherein the content of EO is 1, 2, 2.5, 3 or 4 mol per tole of fatty alcohol ether sulfate, and in which M is sodium or potassium.

In secondary alkanesulfonates, the alkyl group can be either saturated or unsaturated, branched or linear and optionally substituted with a hydroxyl group.

The sulfo group can be at any position on the C chain, the primary methyl groups at the beginning and end of the chain having no sulfonate groups. The preferred secondary alkanesulfonates contain linear alkyl chains with about 9 to 25 carbon atoms, preferably about 10 to about 20 carbon atoms and particularly preferably about 13 to 17 carbon atoms. The cation is, for example, sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium, and mixtures thereof. Sodium as the cation is preferred.

In addition to secondary alkanesulfonates, primary alkanesulfonates can also be used in the detergents according to the invention.

The preferred alkyl chains and cations correspond to those of the secondary

Alkanesulfonates.

The preparation of primary alkanesulfonic acid from which the corresponding sulfonates which act as surfactants are obtained is e.g. described in EP 854 136 A1.

Other suitable anionic surfactants are alkenyl or alkylbenzenesulfonates.

The alkenyl or alkyl group can be branched or linear and optionally substituted with a hydroxyl group. The preferred alkylbenzenesulfonates contain linear alkyl chains with about 9 to 25 carbon atoms, preferably from about 10 to about 13 carbon atoms, the cation is sodium, potassium, ammonium,

Mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. Magnesium is preferred as the cation for mild surfactant systems, while sodium is preferred for standard washing applications. The same applies to alkenylbenzenesulfonates.

The term anionic surfactants also includes olefin sulfonates which are obtained by sulfonating C8-C ₂₄ -, preferably C ₄ -C ₆ -σ-olefins with sulfur trioxide and subsequent neutralization. Due to the manufacturing process, these olefin sulfonates can contain smaller amounts of hydroxyalkanesulfonates and alkane disulfonates. Special mixtures of olefin sulfonates are described in US 3,332,880.

Other preferred anionic surfactants are carboxylates, e.g. Fatty acid soaps and comparable surfactants. The soaps can be saturated or unsaturated and can contain various substituents such as hydroxyl groups or or-sulfonate groups. Linear saturated or unsaturated hydrocarbon radicals are preferred as the hydrophobic portion with approximately 6 to approximately 30, preferably approximately 10 to approximately 18 carbon atoms.

Other suitable anionic surfactants are salts of acylaminocarboxylic acids, the acyl sarcosinates formed in the alkaline medium by reaction of fatty acid chlorides with sodium sarcosinate; Fatty acid-protein condensation products obtained by reacting fatty acid chlorides with oligopeptides; Salts of alkyl sulfamidocarboxylic acids; Salts of alkyl and alkylaryl ether carboxylic acids; sulfonated polycarboxylic acids prepared by sulfonating the pyrolysis products of alkaline earth metal citrates, as described, for example, in GB-1, 082, 179; Alkyl and Alkenylglycerinsulfate as Oleylglycerin- sulfates, alkylphenol ether sulfates, alkyl phosphates, alkyl ether phosphates, isethionates such as the acyl isethionates, N-acyl taurides, alkyl succinates, sulfosuccinates, Monoester of sulfosuccinates (especially saturated and unsaturated Ci2-Cι ₈ monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C ₁ 2-C ₁ 8-diesters), acyl sarcosinates, sulfates of alkyl polysaccharides such as sulfates of alkyl polyglycosides, branched primary alkyl sulfates and alkyl polyethoxy carboxylates such as those of the formula RO (CH2CH2) kCH ₂ COO ^" M ⁺ , where RC ₈ to C ₂₂ alkyl, k is a number from 0 to 10 and M is a cation. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II, Schwartz, Perry and Berch).

Nonionic surfactants

Condensation products of aliphatic alcohols with approx. 1 to approx. 25 mol ethylene oxide.

The alkyl chain of the aliphatic alcohols can be linear or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.

The condensation products of C-io to C2o alcohols with about 2 to about 18 moles of ethylene oxide per mole of alcohol are particularly preferred. The alkyl chain can be saturated or unsaturated. The alcohol ethoxylates can have a narrow ("narrow range ethoxylates") or a broad homolog distribution of the ethylene oxide ("broad range ethoxylates").

Examples of commercially available nonionic surfactants of this type are Tergitol ^® 5-S-9 (condensation product of a linear secondary C ₁₁ -C ₁ 5 alcohol with 9 mol ethylene oxide), Tergitol ^® 24-L-NMW (condensation product of a linear primary Cι ₂ -Cι -Alcohol with 6 mol of ethylene oxide at close

Molecular weight distribution). The Genapol ^® brands of Clariant GmbH also fall under this product class.

Condensation products of ethylene oxide with a hydrophobic base, formed by the condensation of propylene oxide with propylene glycol.

The hydrophobic part of these compounds preferably has a molecular weight between approximately 1500 and approximately 1800. The addition of ethylene oxide to this hydrophobic part leads to an improvement in water solubility. The product is liquid up to a polyoxyethylene content of approx. 50% of the total weight of the condensation product, which corresponds to a condensation with up to approx. 40 mol ethylene oxide. Commercially available examples of this product class are the Pluronic ^® brands from BASF and the ^® Genapol PF brands from Clariant GmbH.

Condensation products of ethylene oxide with a reaction product of propylene oxide and ethylenediamine.

The hydrophobic unit of these compounds consists of the reaction product of ethylenediamine with excess propylene oxide and generally has a molecular weight of approximately 2500 to 3000. Ethylene oxide is added to this hydrophobic unit up to a content of approximately 40 to approximately 80% by weight of polyoxyethylene and a molecular weight of approximately 5000 to 11000. Commercially available examples of this class of compounds are the ^® Tetronic brands from BASF and the ^® Genapol PN brands from Clariant GmbH.

Semipolar nonionic surfactants

This category of nonionic compounds includes water-soluble amine oxides, water-soluble phosphine oxides and water-soluble sulfoxides, each with an alkyl radical of approximately 10 to approximately 18 carbon atoms. Semipolar nonionic surfactants are also amine oxides of the formula O

R (OR?) _Χ N (R ¹ ) ₂

R is an alkyl, hydroxyalkyl or alkylphenol group with a chain length of about 8 to about 22 carbon atoms, R ² is an alkylene or hydroxyalkylene group with about 2 to 3 carbon atoms or mixtures thereof, each R ¹ is an alkyl - Or hydroxyalkyl group with approx. 1 to approx. 3 carbon atoms or a polyethylene oxide group with approx. 1 to approx. 3 ethylene oxide units and x means a number from 0 to approx. 10. The R ¹ groups can be connected to one another via an oxygen or nitrogen atom and thus form a ring. Amine oxides of this type are especially C ₁ 0-C ₁ 8 alkyl dimethyl amine oxides and C ₈ -Cι ₂ -Alkoxiethyl-dihydroxyethylamine. fatty acid amides

Fatty acid amides have the formula o ^R c N (R ¹ ) ₂

wherein R is an alkyl group with about 7 to about 21, preferably about 9 to about 17 carbon atoms and each radical R ^{1 is} hydrogen, C ¹ -C ₄ alkyl, C 1 -C ₄ hydroxyalkyl or (C ₂ H ₄ 0) χH means, where x varies from approx. 1 to approx. 3. Cs-C ₂ o-amides, monoethanolamides, diethanolamides and isopropanolamides are preferred.

Further suitable nonionic surfactants are alkyl and alkenyl oligoglycosides as well as fatty acid polyglycol esters or fatty amine polyglycol esters each having 8 to 20, preferably 12 to 18 carbon atoms in the fatty alkyl radical, alkoxylated triglycamides, mixed ethers or mixed formyls, alkyl oligoglycosides, alkenyl oligoglycosides, fatty acid n-phospholoxides, and fatty acid-N-alkylgloxides, protein.

Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols.

These compounds include the condensation products of alkylphenols having a Cβ to C ₂ o alkyl group, which may be either linear or branched, with alkene oxides. Compounds with about 5 to 25 mol of alkene oxide per mol of alkylphenol are preferred. Commercially available surfactants of this type are, for example, Igepal ^® CO-630, Triton ^® X-45,

X-114, X-100 and X102, and the ^® Arkopal-N brands from Clariant GmbH. These surfactants are referred to as alkylphenol alkoxylates, for example alkylphenol ethoxylates. Zwitterionic surfactants

Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkylamide betaines, aminopropionates, aminoglycinates, or amphoteric imidazolinium compounds of the formula

wherein R ^{1 is} C ₈ -C ₂₂ alkyl or alkenyl, R ^{2 is} hydrogen or CH ₂ C0 ₂ M, R ³ CH ₂ CH ₂ OH or CH ₂ CH ₂ θCH ₂ CH ₂ Cθ ₂ M, R ^{4 is} hydrogen, CH ₂ CH ₂ OH or CH2CH ₂ COOM, Z means CO ₂ M or CH ₂ CO ₂ M, n 2 or 3, preferably 2, M is hydrogen or a cation such as alkali metal, alkaline earth metal, ammonium or alkanolammonium.

Preferred amphoteric surfactants of this formula are monocarboxylates and dicarboxylates. Examples include cocoamphocarboxypropionate,

Cocoamidocarboxypropionic acid, Cocoamphocarboxyglycinat (or also known as Cocoamphodiacetat) and Cocoamphoacetat.

Further preferred amphoteric surfactants are alkyldimethylbetaines ( ^® Genagen LAB / Clariant GmbH) and alkyldipolyethoxybetaines with an alkyl radical with about 8 to about 22 carbon atoms, which can be linear or branched, preferably with 8 to 18 carbon atoms and particularly preferably with about 12 to about 18 carbon atoms.

Suitable cationic surfactants are substituted or unsubstituted straight-chain or branched quaternary ammonium salts of the type R ¹ N (CH ₃ ) ₃ ⁺ X ^" , R ¹ R ² N (CH ₃ ) ₂ ⁺ X ^' , R ¹ R ² R ³ N (CH ₃ ) ⁺ X ^" or RR ² R ³ R ⁴ N ⁺ X ^" . The radicals R ¹ , R ² , R ³ and R ⁴ can preferably independently of one another unsubstituted alkyl having a chain length between 8 and 24 carbon atoms, in particular between 10 and 18 C- Atoms, hydroxyalkyl with approx. 1 to approx. 4 carbon atoms, phenyl, C ₂ - to C ₈ -alkenyl, C ₇ - to C ₂₄ -aralkyl, (C ₂ H ₄ 0) _x H, where x is from approx. 1 to about 3 means one or more alkyl groups containing ester groups or cyclic quaternary ammonium salts. X is a suitable anion.

Other detergent ingredients that may be included in the present invention include inorganic and / or organic builders to reduce the hardness of the water. These builders can be present in the detergent and cleaning agent compositions in a proportion by weight of about 5% to about 80%.

Inorganic builders include, for example, alkali, ammonium and alkanolammonium salts of polyphosphates such as tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates, phosphonates, silicates, carbonates including bicarbonates and sesquicarbonates, sulfates and aluminosilicates.

Examples of silicate builders are the alkali metal silicates, in particular those with a SiO ₂ : Na ₂ O ratio between 1.6: 1 and 3.2: 1, and sheet silicates, for example sodium sheet silicates, as described in US Pat. No. 4,664,839, available from Clariant GmbH under the SKS ^® brand. SKS-6 ^® is a particularly preferred layered silicate builder.

Aluminosilicate builders are particularly preferred for the present invention. These are, in particular, zeolites with the formula Naz [(AlO 2) _z (SiO ₂ ) y] -xH ₂ O, where z and y are integers of at least 6, the ratio of z to y between 1.0 and approximately 0.5, and x represents an integer from about 15 to about 264.

Suitable ion exchangers based on aluminosilicate are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally occurring or synthetic. Methods for the production of ion exchangers based on aluminosilicate are described in U.S. 3,985,669 and U.S. 4,605,509. Preferred ion exchangers based on synthetic crystalline aluminosilicates are available under the names Zeolite A, Zeolite P (B) (including those disclosed in EP-A-0 384 070) and Zeolite X. Preferred are aluminosilicates with a particle diameter between 0.1 and 10 m.

Suitable organic builders (co-builders) include polycarboxyl compounds, such as, for example, ether polycarboxylates and oxydisuccinates, as described, for example, in US Pat. Nos. 3,128,287 and 3,635,830. Reference should also be made to “TMS / TDS” builders from US 4,663,071.

Other suitable builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the alkali, ammonium and substituted ammonium salts of polyacetic acids such as e.g. Ethylenediamine-tetraacetic acid and nitrilotriacetic acid, and also polycarbonic acids, such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1, 3,5-tricarboxylic acid, carboxymethyl-oxysuccinic acid, and their soluble salts.

Important organic builders are also polycarboxylates based on acrylic acid and maleic acid, e.g. the Sokalan CP brands from BASF.

Citrate-based builders, e.g. Citric acid and its soluble salts, in particular the sodium salt, are preferred polycarboxylic acid builders which can also be used in granulated formulations, in particular together with zeolites and / or layered silicates.

Other suitable builders are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in US 4,566,984. If phosphorus-based builders can be used, and especially if hand soap bars are to be formulated for washing, various alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1, 1-diphosphonate and other known phosphonates such as those disclosed in, for example, US-3,159,581, US-3,213,030, US-3,422,021, US-3,400,148 and US-3,422,137 can also be used.

The detergents and cleaning agents which contain the combination of a color fixing agent and a soil release polymer according to the invention can furthermore contain the customary auxiliaries which enhance the cleaning action, serve to care for the textile to be washed or change the performance properties of the detergent composition.

Suitable auxiliaries include the substances mentioned in US Pat. No. 3,936,537, for example enzymes, in particular proteases, lipases, cellulases and amylases, mannanases, enzyme stabilizers, foam boosters, foam retardants, tarnishing and / or corrosion inhibitors, suspending agents, dyes, color transfer inhibitors, fillers, optical brighteners .

Disinfectants, alkalis, hydrotropic compounds, antioxidants, perfumes, solvents, solubilizers, redeposition inhibitors, dispersants, processing aids, plasticizers and antistatic agents.

The detergent compositions of the present invention may optionally contain one or more conventional bleaches, as well as bleach activators, bleach catalysts and suitable stabilizers. In general, it must be ensured that the bleaching agents used are compatible with the detergent ingredients. Conventional test methods, such as the determination of the bleaching activity of the formulated cleaning agent depending on the storage time, can be used for this purpose. Peroxyacids can either be used as free peroxyacids, or a combination of an inorganic persalt, e.g. sodium perborate or sodium percarbonate, and an organic peroxyacid precursor can be used.

The organic peroxyacid precursors are often referred to in the art as bleach activators.

Examples of suitable organic peroxyacids are disclosed in U.S. 4,374,035, U.S. 4,681,592, U.S. 4,634,551, U.S. 4,686,063, U.S. 4,606,838 and U.S. 4,671,891.

Examples of compositions suitable for bleaching laundry and containing perborate bleaches and activators are described in U.S. 4,412,934, U.S. 4,536,314, U.S. 4,681, 695 and U.S. 4,539,130.

Examples of peroxyacids preferred for use in this invention include peroxydodecanedioic acid (DPDA), nonylamide of peroxysuccinic acid (NAPSA), nonylamide of peroxyadipic acid (NAPAA) and decyldiperoxysuccinic acid (DDPSA), nonanoyl-amidocaproyloxonic acid and oxy-benzoic acid Alkanoyloxybenzenesulfonic acids such as nonanoyloxybenzenesulfonic acid (NOBS) and lauroyloxybenzenesulfonic acid (LOBS).

Bleaching systems based on a persalt such as perborates or percarbonates with the bleach activator tetraacetylethylene diamine (TAED) are particularly preferably used in the detergents and laundry treatment agents according to the invention. Examples

The following liquid detergent formulations A, B and C were prepared (see Table 1).

Formulation A serves as a reference. Formulation B additionally contains a color fixative and formulation C contains the combination according to the invention of a color fixative with a soil release polymer.

Table 1: Composition of the liquid detergent in% by weight

The dirt reduction position was examined on cotton fabric wfk 10 A, cotton / polyester blend fabric wfk 20 A and polyester fabric wfk 30 A in a Miele household washing machine.

Structure of the commercial products used:

TexCare DFC 6: polyamine derivative. Color fixative for detergents / Fa. Clariant TexCare SRN-170: Nonionic Soil Release Polyester / Fa. Clariant

For this purpose, the test fabric with the detergent formulations was subjected to multiple washings with the addition of standardized test dirt wfk pigment dirt 09V (see Table 2). Table 2: Washing conditions

The whiteness of the test fabrics at the beginning, after five, 10 and 15 washing cycles was determined as a measure of the dirt reduction position. The higher the whiteness, the lower the dirt reduction position.

Table 3: Whiteness of cotton wfk 10 A after multiple washing

Table 4: Whiteness of cotton / polyester wfk 20 A after multiple washing

Table 5: Whiteness of polyester wfk 30 A after multiple washing

Claims

claims:

1. washing and cleaning agents containing a color fixing agent from a) reaction products of polyamines with cyanamides and organic and / or inorganic acids or cyanamides with aldehydes and ammonium salts or cyanamides with aldehydes and amines or amines with epichlorohydrin, b) the group of polyamines and polyamine derivatives, c) the group of polyimines and polyimine derivatives, d) the group of cationic polyelectrolytes, e) the group of polymers containing imidazoline units or f) the group of bischlormethylbiphenylpolyquats and a soil release polymer.

2. Detergent and cleaning agent according to claim 1, wherein the soil release polymer is a water-soluble or water-dispersible polyester.

3. Detergent and cleaning agent according to claim 1, wherein the soil release polymer is a water-soluble or water-dispersible polyester with a molecular weight of less than 20,000, preferably less than 10,000 and very particularly preferably less than 5,000.

4. Detergent and cleaning agent according to claim 1, wherein the soil release polymer is a water-soluble or water-dispersible polyester which is end-capped by alkyl polyalkylene glycols.

5. Detergent and cleaning agent according to claim 1, wherein the soil release polymer is a water-soluble or water-dispersible polyester which is end-capped by methyl polyethylene glycols, the number of ethylene glycol units </ = 90, preferably </ = 50 and particularly preferably </ = 20.

6. washing and cleaning agent according to claim 1, wherein the soil release polymer is one of the water-soluble or water-dispersible polyester, the

</ = 60% by mass and particularly preferably </ = 50% by mass of esterified terephthalic acid units.

7. Washing and cleaning agent according to claim 1, wherein the soil release polymer is a water-soluble or water-dispersible polyester which contains ethylene glycol or polyethylene glycol units.

8. washing and cleaning agent according to claim 1, wherein the soil release polymer is a water-soluble or water-dispersible polyester containing propylene glycol or polypropylene glycol units.

9. washing and cleaning agent according to claim 1, wherein the soil release polymer is a water-soluble or water-dispersible polyester which contains both ethylene glycol or polyethylene glycol, and also propylene glycol or polypropylene glycol units.

10. washing and cleaning agent according to claim 1, wherein the soil release polymer is a water-soluble or water-dispersible polyester which is anionically modified by means of condensed sulfoisophthalic acid and / or glycerol sulfoethyl ether units.

11. Washing and cleaning agent according to claim 1, wherein the soil release polymer is a water-soluble or water-dispersible polyester which is end-capped with ethylene oxide by means of isethionic acid, hydroxypropanesulfonic acid or their reaction products.

12. Detergent and cleaning agent according to claim 1, wherein the soil release polymer is a cellulose ether.

13. Washing and cleaning agent according to claim 1, wherein the soil release polymer is a methylhydroxyethyl cellulose.

14. Washing and cleaning agent according to claim 1, wherein the soil release polymer is a methylhydroxypropyl cellulose.

15. Washing and cleaning agent according to claim 1, wherein the soil release polymer is a methyl cellulose.

16. Washing and cleaning agent according to claim 1, wherein the soil release polymer is a cellulose ether with a molecular weight of less than 150,000.

17. Detergent and cleaning agent according to claim 1, wherein the ratio of color fixing agent to soil release polymer is 1:10 to 10: 1, preferably 1: 5 to 5: 1.

18. Washing and cleaning agent according to claim 1, wherein the

Use concentration of the combination of color fixative and soil release polymer in the detergent 0.1 to 20% by weight, preferably 0.1 to 10% by weight and particularly preferably 0.1 to 5% by weight, very particularly preferably 0.3 is up to 3% by weight.